CN102449003B - Film made from heterogeneous ethylene/alpha-olefin interpolymer - Google Patents

Film made from heterogeneous ethylene/alpha-olefin interpolymer Download PDF

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CN102449003B
CN102449003B CN2009801595952A CN200980159595A CN102449003B CN 102449003 B CN102449003 B CN 102449003B CN 2009801595952 A CN2009801595952 A CN 2009801595952A CN 200980159595 A CN200980159595 A CN 200980159595A CN 102449003 B CN102449003 B CN 102449003B
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film
interpretation
density
polymkeric substance
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CN102449003A (en
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云小兵
R.瓦斯蒂亚尼
H.L.戈
吴昶
M.德米罗尔斯
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/622—Component covered by group C08F4/62 with an organo-aluminium compound
    • C08F4/6222—Component of C08F4/62 containing at least two different metals
    • C08F4/6224—Component of C08F4/62 containing at least two different metals containing magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/63—Pretreating the metal or compound covered by group C08F4/62 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/632—Pretreating with metals or metal-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/02—Low molecular weight, e.g. <100,000 Da.
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/08—Low density, i.e. < 0.91 g/cm3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/26—Use as polymer for film forming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Abstract

A multilayer film is disclosed, comprising at least two layers, wherein a first layer comprises a first interpolymer of ethylene and at least one alpha-olefin, characterized wherein the first interpolymer has a density of less than 0.925 g/cm3, and an average Mv and a valley temperature between the interpolymer and high crystalline fraction, The, such that the average Mv for a fraction above The from ATREF divided by average Mv of the whole polymer from ATREF (Mhc/Mhp) is less than about 1.95 and wherein the first interpolymer has a CDBI of less than 60%, and wherein at least one other second layer comprises a second interpolymer of ethylene and at least one alpha-olefin, wherein the second interpolymer has a density from 0.925 to 0.965 g/cm3. The interpolymer of ethylene and at least one alpha-olefin can also be characterized as having a high density (HD) fraction and an overall density such that % HD fraction < 0.0168x2 - 29.636x + 13036 where x is the density in grams/cubic centimeter. Fabricated articles such as stand up pouches comprising the novel multilayer films are also disclosed.

Description

The film of being made by heterogeneous ethylene/alpha-olefin interpolymer
The cross reference of related application
The application requires the right of priority of the United States serial 61/165,065 of submission on March 31st, 2009.
Background technology
There is the film of high transparent, high rigidity and high dart impact at packaging industry camber needs.The transparency is brought aesthetic properties, and high rigidity and high dart provide and subtract thick character.
For the final user, can manufacture the ethene-alpha-olefin copolymer resin of film of aesthetic feeling (optics) with improvement and anti-physical abuse (dart) character or the membrane structure that comprises these resins and produce and be worth.Non-homogeneous ethene-alpha-olefin copolymer has high crystalline (thick crystalline substance (thick crystals)) fraction and multipolymer (Bao Jing (thin crystals)) fraction (fractions) simultaneously.
The optical property of film can be according to surface gloss (gloss), mist degree (haze) and transparency (clarity) definition.Mist degree can be depending on internal haze (main body scattering) and outside mist degree (surface scattering).The two all can change outside mist degree and internal haze along with high crystalline fraction content and the high crystalline fraction molecular weight of the resin for the manufacture of film.The high crystalline fraction can be comprised of the thick crystalline substance of scattered light, so the raising of high crystalline fraction content can improve mist degree and the infringement optical property of film.The molecular weight that reduces the high crystalline fraction can improve the thickness of crystal in the high crystalline fraction.High crystalline fraction crystal is thicker, and the film optical property is poorer.Therefore the reduction of the content of high crystalline fraction and raising molecular weight are desirable for improving optical property, but, due to high melt elasticity, too high molecular weight can cause the melt fracture problem.In addition, the molecular weight that improves the high crystalline fraction for improving optical property can damage the dart character of film.The higher molecular weight of multipolymer fraction is desirable for higher film dart.For specific resin melt index (MI or I 2), improve the molecular weight of high crystalline fraction for improving optical property and have to carry out balance by the molecular weight that reduces the multipolymer fraction, make MI keep constant.The reduction of molecular weight of copolymer will damage dart character.Therefore for dart character and the optical property of balance, best high crystalline fraction molecular weight is desirable.The thick crystalline substance of high crystalline fraction provides intensity for film, thereby improves its character of tearing.
Therefore, reduce the high crystalline fraction content and can damage the film lancinating for improving optical property.For realizing the balance of lancinating and optical property, need the optimum content of high crystalline fraction.
The surperficial mist degree of film can be depending on the molecular weight distribution of ethene-alpha-olefin copolymer.The molecular weight distribution of non-constant width usually improves the melt elasticity of resin and causes surperficial melt fracture, and very narrow molecular weight distribution can cause processing problems and cause surperficial melt fracture at the die head place.Due to the optical property of the existence of surperficial melt fracture infringement film, institute thinks that improving optical property also needs optimum weight to distribute.
The dart character of film can be depending on molecular weight distribution and multipolymer fraction content.Molecular weight distribution is narrower and the multipolymer fraction content is higher, and the film dart is just higher.Too narrow molecular weight distribution can be damaged optical property and processing characteristics (film manufacture), therefore for obtaining the balance of processing characteristics, dart character and optical property, needs optimum weight to distribute.In addition, can realize the raising of multipolymer fraction content, but cost is the reduction of high crystalline fraction content, this can damage the film lancinating.Therefore, in order to realize processing characteristics, dart character, to tear the well balanced of character and optical property, need the particular combination of molecular weight distribution and high crystalline and multipolymer fraction content.
The rigidity of film depends on resin density.Resin density is higher, and the crystallinity fraction is just more, so membrane rigidity is just higher.Yet as discussed above, the high crystalline fraction will be damaged film optical property and dart impact, therefore, membrane rigidity and film optical property/dart impact are the character of mutually repelling.
The present invention is multilayer film, and its specific resin family by this particular combination with molecular weight distribution and high crystalline and multipolymer fraction content and molecular weight manufactures.For equal density and melt index, this combination of resin feature provides optical property, the rigidity with improvement, dart character, tears the film of character and processing characteristics.
Summary of the invention
In one embodiment, the claimed multilayer film that comprises at least two layers, the first interpretation that wherein the first layer comprises ethene and at least one alpha-olefin, be characterised in that wherein said the first interpretation has the 0.925g/cm of being less than 3density, and average M vand the paddy temperature between interpretation and high crystalline fraction (valley temperature), T hc, make from ATREF higher than T hcthe average M of fraction vaverage M divided by the whole polymkeric substance of ATREF v(M hc/ M hp) be less than approximately 1.95, preferably be less than 1.7, and wherein said the first interpretation has the CDBI that is less than 60%, and the second interpretation that wherein at least one other second layer comprises ethene and optional at least one alpha-olefin, wherein said the second interpretation has 0.925-0.965g/cm 3density, the preferred non-homogeneous branching of wherein said the first interpretation, also preferably wherein said the first interpretation has the CDBI that is less than 55%.
In another embodiment, the present invention is film, and the layer that it comprises at least one the first interpretation that comprises ethene and at least one alpha-olefin, be characterised in that wherein said the first interpretation has the 0.925g/cm of being less than 3density and be characterized as there is high-density (HD) fraction and global density, make the percentage ratio<0.0168x of HD fraction 2-29.636x+13036, wherein x in g/cc global density, and other layer of at least one the second interpretation that comprises ethene and optional at least one alpha-olefin, wherein said the second interpretation has 0.925-0.965g/cm 3density.
In arbitrary embodiment, described film can be skin A/ core/skin B layer, and preferably wherein skin A and skin B comprise identical ethene interpretation, more preferably the first interpretation described in each two embodiments above self-contained of skin A and skin B wherein.
In addition in arbitrary embodiment, the film of 120 microns can have according to ASTM D 1003, measure<16% mist degree, especially combination has the dart B (Dart B) of at least 250 grams that use ASTM D 1709 to measure, with 2% secant modulus ((MD+CD)/2) of at least 240MPa measured according to ASTM D882, and the ultimate tensile strength of 45Mpa at least on MD and CD direction of measuring according to ASTM D882.
The film of arbitrary embodiment also can comprise at least one other natural or synthetic polymer, and preferred wherein said synthetic polymer is Low Density Polyethylene.
Preferably, described the first interpretation comprises about 0.1g/10min to the melt index of about 10g/10min and/or comprises and is less than about 0.922g/cm 3global density.
Also preferably, described the first interpretation comprises every 1000 C atoms and is less than the long chain branches of 1 and/or is less than approximately 5 molecular weight distribution M w/ M n.
The goods that comprise above-mentioned film as durable bags (stand up pouch) also in the scope of embodiment of the present invention.
Preferably, described the second interpretation comprises melt index and/or the comprise>0.925g/cm of about 0.1g/10min to about 10g/10min 3global density.
Also preferably, described the second interpretation is included in the high crystalline fraction non-homogeneous LLDPE or the HDPE resin with high MW.
Also preferably, described the second interpretation has every 1000 C atoms and is less than the long chain branches of 1 and/or is less than approximately 5 molecular weight distribution M w/ M n.
The goods that comprise above-mentioned film as durable bags also in the scope of embodiment of the present invention.
Above-mentioned film embodiment (wherein the first interpretation is crosslinked at least partly, reaches at least 5 % by weight gellings) also within the scope of the present invention.
The accompanying drawing explanation
Fig. 1 illustrates the short-chain branched distribution from ATREF and the log Mv data of resin embodiment 1 of the present invention and resin comparative examples 1.
Embodiment
The resin that has the unique combination of molecular weight distribution and high crystalline and multipolymer fraction content by use, realized the balance of rigidity, processing characteristics, dart character, tensile property and optical property.Resin feature and film character details are listed in table 1, Fig. 1, table 2 and table 3.The high-density fraction content significantly reduces and the multipolymer fraction content improves.High crystalline fraction viscosity-average molecular weight reduces the ratio of whole polymer viscosity molecular-weight average, shows that the molecular weight of high crystalline fraction is lower.Multipolymer fraction viscosity-average molecular weight improves the ratio of whole polymer viscosity molecular-weight average, shows that the molecular weight of multipolymer fraction is higher.These difference of resin feature realize by the following method: reducing temperature of reaction, reach approximately 160 ℃ to approximately 180 ℃, be especially 175 ℃, and reduce the Al/Ti molar ratio, reach approximately 1: 1 to approximately 5: 1, is especially 1: 1 to approximately 2.5: 1.
The film of being made by the resin of the present invention of the unique combination with characterization of molecules has dart and the optical property of remarkable improvement, and sacrifice any MD, does not tear and processing characteristics.
This resin can be used for such application, wherein needs the improvement of optics and dart character, and expendable film is not torn the processing characteristics in character and film manufacture.
Low reaction temperatures can be used for the molecular weight distribution that narrows.The temperature of reaction of 175 ℃ obtains having the product of narrow molecular weight distributions, and does not significantly reduce turnout (lb/hr).
The significant further reduction of the temperature molecular weight distribution that can further narrow, but the processing characteristics (film manufacture) that significantly reduces turnout and make product infringement resin.
Low Al/Ti ratio can be used for narrowing molecular weight distribution and for reducing the high crystalline fraction with improve the multipolymer fraction.For the HEC-3 catalyzer with 3.0Ti/Mg ratio, the Al/Ti ratio of 1.5: 1 obtains having narrow molecular weight distributions, the product of less high crystalline fraction and more multipolymer fraction, and not remarkably influenced reaction stability.
Preferably, temperature of reaction is approximately 160 ℃ to approximately 180 ℃.
Preferably, the ratio of aluminum metal atom (being preferably Al/Ti) is approximately 1: 1 to approximately 5: 1.
The melt index of the vinyl-type polymer (ethylenic polymer) disclosed can be about 0.01g/10 minute to about 1000g/10 minute, by ASTM 1238-04 (2.16kg and 190 ℃), measures.
polymkeric substance based on ethene
Can prepare with Ziegler-Natta catalyst by the polymkeric substance based on ethene be applicable to.
The example of the linear polymkeric substance based on ethene comprises high density polyethylene(HDPE) (HDPE) and linear low density polyethylene (LLDPE).Applicable polyolefine includes but not limited to ethene/diene interpretation, ethylene/alpha-olefin interpolymers, Alathon and blend thereof.
The interpretation of non-homogeneous linearity based on ethene be applicable to for the second interpretation comprises linear low density polyethylene (LLDPE).For example, some interpretations that use Ziegler-Natta catalyst to prepare have about 0.925g/cm 3to about 0.94g/cm 3density and there is about 0.01g/10 minute to approximately 1, the melt index (I of 000g/10 minute 2), by ASTM 1238-04 (2.16kg and 190 ℃), measure.Preferably, described melt index (I 2) can be about 0.1g/10 minute to about 50g/10 minute, and density is higher than 0.925g/cm 3.The polymkeric substance of non-homogeneous linearity based on ethene can have approximately 3.5 to about 5 molecular weight distribution M w/ M n.
The polymkeric substance of described linearity based on ethene can comprise the unit derived from one or more alpha-olefin copolymers, as long as comprise the polymerising ethylene unit of at least 50 % by mole in polymkeric substance.
High density polyethylene(HDPE) (HDPE) also is suitable for the second interpretation and can has about 0.94g/cm 3to about 0.97g/cm 3density.HDPE is generally the interpretation of one or more alpha-olefin comonomer of Alathon or ethene and low levels.With respect to the various multipolymers of ethene and one or more alpha-olefin comonomer, HDPE contains relatively few side chain.HDPE can comprise the unit derived from one or more alpha-olefin comonomer that is less than 5 % by mole.
As contrary as LDPE with the polymkeric substance based on ethene of the high branching of conventional low-crystallinity, there is not long chain branching in the linear polymkeric substance based on ethene as linear low density polyethylene and ultra-low density polyethylene (ULDPE) are characterised in that.The polymkeric substance of non-homogeneous linearity based on ethene can be through ethene and one or more alpha-olefin comonomer in the situation that do not exist solution, slurry or the vapour phase polymerization preparation of Ziegler-Natta catalyst as LLDPE, for example, by United States Patent (USP) 4, the method disclosed in 076,698 people such as () Anderson.The preparation method's of the material of these classifications and they relevant discussion can be referring to United States Patent (USP) 4,950,541 people such as () Tabor.Prepare other patent of LLDPE and openly comprise WO2008/0287634, US 4198315, US 5487938, EP 0891381 and US 5977251.
Alpha-olefin comonomer can have, for example, and 3-20 carbon atom.Preferably, described alpha-olefin comonomer can have 3-8 carbon atom.Exemplary alpha-olefin comonomer includes but not limited to propylene, 1-butylene, 3-methyl-1-butene, 1-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 4,4-dimethyl-1-amylene, 3-ethyl-1-amylene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene.The commercial embodiments of the linear polymkeric substance (it is interpretation) based on ethene comprises ATTANE tMextremely-low density linear polyethylene copolymer, DOWLEX tMpolyvinyl resin and FLEXOMER tMvery low density polyethylene, all can derive from The Dow Chemical Company.
Aspect another, when mentioning that Alathon (, therefore containing any comonomer and without the high density ethylene homopolymers of short chain branch) while using, term " homogeneous ethylene polymer (homogeneous ethylene polymer) " or " evenly linear tetrafluoroethylene polymer (homogeneous linear ethylene polymer) " can be used for describing this polymkeric substance.
The ethene polymers that the described polymkeric substance based on ethene that is suitable for the first interpretation of the application is relatively non-homogeneous (inhomogeneous) (or non-homogeneous (heterogeneous)), it has short chain branch and is characterised in that relatively low composition Tile Width index (composition distribution breadth index) (CDBI).That is, described ethene polymers has and is less than or equal to approximately 60%, preferably is less than or equal to approximately 55%, is more preferably less than or equals approximately 50% CDBI, but usually comprising measurable high-density (crystallinity) polymer fractions.
CDBI is defined as 50% weight percentage with interior polymer molecule of co-monomer content in total mole of co-monomer content of intermediate value, and the contrast of the comonomer distribution in the expression polymkeric substance and the comonomer distribution that distribution is estimated for Bernoullian.Polyolefinic CDBI can calculate from the data that derive from technology known in the art expediently, for example, and temperature rising elution classification (" TREF "), as with as described in Publication about Document: the people such as Wild, Journal of Polymer Science, Poly.Phys.Ed., Vol.20,441 (1982); L.D.Cady, " comonomer type and be distributed in the effect (The Role of Comonomer Type and Distribution in LLDPE Product Performance) in the LLDPE product performance ", SPE Regional technical Conference, Quaker Square Hilton, Akron, OH, 107-119 (Oct.1-2,1985); Or United States Patent (USP) 4,798,081 (people such as Hazlitt) and United States Patent (USP) 5,008,204 (Stehling).Yet the TREF technology does not comprise the amount of purification in CDBI calculates.More preferably, the comonomer distribution of polymkeric substance is used 13c NMR analyzes according to for example with the technical measurement described in Publication about Document: United States Patent (USP) 5,292,845 people such as () Kawasaki and Rev.Macromol.Chem, Phys., C29,201-317 (J.C.Randall).
In Alathon, the existence of long chain branching can be by being used 13c nucleus magnetic resonance (NMR) spectrographic determination and use Randall (Rev.Macromol.Chem.Phys., C29, V.2& 3,285-297) described method quantizes.Existence can be used for being determined at other known technology of the existence of long chain branches in ethene polymers (comprising ethene/1-octene interpretation).Two this illustrative methods are the gel permeation chromatography (GPC-LALLS) be connected with the low angle laser light scattering detector and the gel permeation chromatography (GPC-DV) be connected with differential viscosity meter detector.The purposes that these technology detect for long chain branches and potential theory record in the literature well.Referring to, for example, Zimm, G.H. and Stockmayer; W.H., J.Chem.Phys., 17,1301 (1949); and Rudin, A., the modernism of polymer characterization (Modern Methods of Polymer Characterization), John Wiley& Sons, New York (1991) 103-112.
Term " non-homogeneous " and " non-homogeneous branching (heterogeneously branched) " mean that ethene polymers can be characterized by and has the mixture of various ethene to the interpretation molecule of comonomer molar ratio.Non-homogeneous branching linear tetrafluoroethylene polymer can be from The Dow Chemical Company as DOWLEX tMlinear low density polyethylene and as ATTANE tMthe ultra-low density polyethylene resin obtains.Non-homogeneous branching linear tetrafluoroethylene polymer can be through ethene and one or more optional alpha-olefin comonomer in the situation that exist solution, slurry or the vapour phase polymerization preparation of Ziegler-Natta catalyst, for example, by United States Patent (USP) 4, the method disclosed in 076,698 people such as () Anderson.Non-homogeneous branched ethylene polymer is characterized by usually has approximately 3 to about 5 molecular weight distribution mw/mn, and therefore, all is being different from substantially linear ethene polymers and even branching linear tetrafluoroethylene polymer forming aspect short-chain branched distribution and molecular weight distribution.
the polymkeric substance based on ethene of height long chain branching
Can use high-pressure process preparation (using free-radical chemistry with polymerizing ethylene monomer) as Low Density Polyethylene (LDPE) with the polymkeric substance based on ethene of the height long chain branching of the application's new non-homogeneous ethene polymers blend.Typical case LDPE density polymer is about 0.91g/cm 3to about 0.94g/cm 3.Low Density Polyethylene can have the melt index (I of about 0.01g/10 minute to about 150g/10 minute 2).The polymkeric substance based on ethene of height long chain branching also can be described as " high pressure ethylene polymer " as LDPE, mean described polymer moieties or fully at pressure higher than 13, in the autoclave of 000psig or tubular reactor, use radical initiator as superoxide homopolymerization or copolymerization (referring to, for example, United States Patent (USP) 4,599,392 (people such as McKinney)).This method produces has the remarkable branch polymkeric substance of (comprising long chain branches).
The polymkeric substance based on ethene of height long chain branching is generally Alathon; Yet described polymkeric substance can comprise the unit derived from one or more alpha-olefin copolymers, as long as comprise the vinyl monomer of the polymerization of at least 50 % by mole in polymkeric substance.
In the polymkeric substance based on ethene of height of formation branching, spendable comonomer includes but not limited to usually have the alpha-olefin comonomer that is no more than 20 carbon atoms.For example, described alpha-olefin comonomer for example can have 3-10 carbon atom, or selectively, described alpha-olefin comonomer for example can have 3-8 carbon atom.Exemplary alpha-olefin comonomer includes but not limited to propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methyl-1-pentene.Selectively, Exemplary comonomers includes but not limited to α, β-undersaturated C 3-C 8-carboxylic acid, be specially toxilic acid, fumaric acid, methylene-succinic acid, vinylformic acid, methacrylic acid and β-crotonic acid, α, β-undersaturated C 3-C 8-carboxylic acid derivative, for example undersaturated C 3-C 15-carboxylicesters, be specially C 1-C 6the ester of-alkanol, perhaps acid anhydrides, be specially methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Tert-butyl Methacrylate, methyl acrylate, ethyl propenoate, n-butyl acrylate, 2-EHA, tert-butyl acrylate, methacrylic acid acid anhydrides, maleic anhydride and methylene-succinic acid acid anhydrides.In addition selectively, described Exemplary comonomers includes but not limited to vinyl carboxylates, for example, and vinyl-acetic ester.In addition selectively, Exemplary comonomers includes but not limited to n-butyl acrylate, vinylformic acid and methacrylic acid.
Method
The first interpretation based on ethene for preparation is used in the present invention, can be used solution phase legal.Typically, this method well-stirred reactor as loop reactor or ball reactor (sphere reactor) in, at approximately 150 ℃ to approximately 300 ℃, preferably approximately 160 ℃ to the about temperature of 180 ℃, and at about 30psi to about 1000psi, preferred about 30psi carries out to the pressure of about 750psi.The residence time in this method is approximately 2 minutes to approximately 20 minutes, preferably approximately 10 minutes to approximately 20 minutes.Ethene, solvent, catalyzer and one or more optional comonomers are continuously supplied to reactor.Exemplary catalysts is in these embodiments drawn together but is not limited to Ziegler-Natta catalyst.Exemplary solvent includes but not limited to isoparaffin.For example, this solvent by name ISOPAR E (ExxonMobil Chemical Co., Houston, Texas) be purchased.Then the mixture of the polymkeric substance based on ethene of gained and solvent is removed and isolating polymer from reactor.Solvent reclaims through solvent recovery unit (that is, heat exchanger and vapor liquid knockout drum (vapor liquid separator drum)) usually, and recirculation is back in paradigmatic system.
For the polymkeric substance based on ethene of preparation height long chain branching, the polymerization of usually using high-pressure free radical to cause.Known two kinds of polymerization types that different high-pressure free radicals causes.In the first kind, use the stirred autoclave container with one or more reaction zones.Described autoclave reactor has several decanting points usually, for initiator or monomer feed, or for the two feed of initiator and monomer.In Second Type, use jacket pipe (jacketed tube) as reactor, it has one or more reaction zones.(but nonrestrictive) reactor length be applicable to can be approximately 100 meters to approximately 3000 meters, is preferably approximately 1000 meters to approximately 2000 meters.For the reactor of arbitrary type, the beginning of reaction zone is injected and is limited by the side of arbitrary reaction initiator, ethene, telomer, one or more comonomers and any combination thereof.High-pressure process can be carried out in autoclave or tubular reactor or in the combination of autoclave and tubular reactor, each self-contained one or more reaction zones of described autoclave and tubular reactor.
The applicable catalyzer used in method embodiment comprises any compound or the compound combination of the polymkeric substance that is suitable for preparing tool composition likely or type (polymkeric substance based on ethene of the polymkeric substance based on ethene or height long chain branching).Can use non-homogeneous catalyzer.In some method embodiment, can use non-homogeneous catalyzer, comprising the Z-N composition of knowing, is especially the group-4 metal halogenide of load on group II metal halogenide or halogenide and the alkoxide of mixing, and the catalyzer based on chromium or vanadium of knowing.In some method embodiment, the catalyzer of use can be even catalyzer, and it comprises relatively pure organometallic compound or metal complex, is especially compound or the complex compound of the metal based on being selected from 3-10 family or group of the lanthanides.Surpass a kind of catalyzer if use in system, so preferably, any catalyzer used does not significantly detrimentally affect the performance of another kind of catalyzer under polymerizing condition.Ideally, under polymerizing condition, catalyst-free is greater than 25% aspect activity decreased, more preferably greater than 10%.
In the method embodiment of utilizing the complexing metal catalyzer, by combining with promotor (be preferably positively charged ion and form promotor, strong lewis acid or its combination), can be by this catalyst activation to form activate catalyst composition.The applicable promotor used comprises polymerization or oligomeric oxidation of alkyl aluminium (aluminoxanes), is especially methyl oxidation aluminum alkyls (methyl aluminoxane), and inertia, compatible, and the ion of non-coordination forms compound.So-called modified methyl oxidation of alkyl aluminium (modified methyl aluminoxane) (MMAO) or triethyl aluminum (TEA) also be suitable for use as promotor.A kind of technology for the preparation of this modified oxidized aluminum alkyls discloses in United States Patent (USP) 5,041,584 people such as () Crapo.Oxidation of alkyl aluminium also can be as United States Patent (USP) 5,542,199 (people such as Lai); 4,544,762 (people such as Kaminsky); 5,015,749 (people such as Schmidt); With 5,041, the preparation disclosed in 585 (people such as Deavenport).
In some method embodiment, also can in embodiment vinyl-type polymer (embodiment ethylenic polymer) product, comprise processing aid, for example softening agent.These auxiliary agents include but not limited to phthalic ester, for example phthalic acid dioctyl ester and o-benzene butyl phthalate ester, natural oil is as lanolin, and the paraffin oil, naphthenic oil and the perfume oil that derive from petroleum refining, and from the liquid resin of rosin or petroleum.The example categories that can be used as the oil of processing aid comprises that white mineral oil is as KAYDOL oil (Chemtura Corp.; Middlebury, Conn.) and SHELLFLEX 371 naphthenic oils (Shell lubricant; Houston, Tex.).Another kind of applicable oil is TUFFLO oil (Lyondell lubricant; Houston, Tex).
In some method embodiment, by one or more stabilizer treatments of embodiment vinyl-type polymer, for example, antioxidant, for example IRGANOX 1010 and IRGAFOS 168 (Ciba Specialty Chemicals; Glattbrugg, Switzerland).Usually, extrude or other melting treatment before with one or more stabilizer treatment polymkeric substance.In other method embodiment, other polymeric additive includes but not limited to UV light absorber, static inhibitor, pigment, dyestuff, nucleator, filler, slip(ping)agent, fire retardant, softening agent, processing aid, lubricant, stablizer, smoke suppressant, viscosity control agent and release agent.In combination weight, embodiment vinyl-type polymer composition can for example comprise one or more additives that are less than 10%, the weight based on the embodiment vinyl-type polymer.
Described embodiment vinyl-type polymer further can be mixed.In some embodiment vinyl-type polymer compositions, one or more antioxidants further can be compounded in polymkeric substance and by the polymkeric substance granulation be mixed.The vinyl-type polymer be mixed can contain one or more antioxidants of any amount.For example, for each 1,000,000 parts of polymkeric substance, the vinyl-type polymer be mixed can comprise approximately 200 to about one or more phenol antioxidant of 600 parts.In addition, for each 1,000,000 parts of polymkeric substance, the vinyl-type polymer be mixed can comprise approximately 800 to the about antioxidant based on phosphorous acid ester of 1200 parts.For each 1,000,000 parts of polymkeric substance, the vinyl-type polymer of the disclosure be mixed can further comprise approximately 300 to the about calcium stearate of 1250 parts.
Linking agent
Some applicable linking agents have been disclosed in in Publication about Document: the people such as Zweifel Hans, " Plastics Additives Handbook, " Hanser Gardner Publications, Cincinnati, Ohio, the 5th edition, the 14th chapter, 725-812 page (2001); Encyclopedia of Chemical Technology, the 17th volume, the 2nd edition, Interscience Publishers (1968); With Daniel Seern, " Organic Peroxides, " the 1st volume, Wiley-Interscience, (1970), by all these documents, mode by reference is incorporated to this paper.
The limiting examples of applicable linking agent comprises the urea of superoxide, phenol, trinitride, aldehyde-amine reaction product, replacement, the guanidine of replacement; The xanthate or the salt (xanthates) that replace; The dithiocarbamate or the salt (dithiocarbamates) that replace; Sulfocompound, for example thiazole, sulfinyl amine, thiuram-disulfide, paraquinonedioxime, dibenzo paraquinonedioxime, sulphur; Imidazoles; Silane and combination thereof.
The limiting examples of applicable organo-peroxide linking agent comprises alkyl peroxide, aryl peroxides, peroxy esters, peroxy carbonates, diacyl peroxide, peroxy ketal, cyclic peroxide and combination thereof.In some embodiments, described organo-peroxide is dicumyl peroxide, tertiary butyl isopropylidene peroxy benzene (t-butylisopropylidene peroxybenzene), 1,1-bis--t-butylperoxy-3,3,5-trimethyl-cyclohexane, 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane, the tertiary butyl-cumyl peroxide, two-tert-butyl peroxide, 2,5-dimethyl-2,5-bis--(t-butylperoxy) hexin or its combination.In one embodiment, described organo-peroxide is dicumyl peroxide.Other instruction about the organo-peroxide linking agent is disclosed in C.P.Park, " polyolefin foam (Polyolefin Foam) ", the 9th chapter of Handbook of Polymer Foams and Technology, D.Klempner and K.C.Frisch edit, Hanser Publishers, the 198-204 page, Munich (1991), by it, mode by reference is incorporated to this paper.
The limiting examples of applicable trinitride linking agent comprises triazo acid ester, for example tetramethylene two (triazo acid ester); The many trinitride of aromatics, for example 4,4 '-the ditan diazide; And sulfuryl azide (sulfonazides), p for example, p '-oxygen di-(benzenesulfonyl trinitride).The disclosure of trinitride linking agent can be referring to United States Patent (USP) 3,284, and 421 and 3,297,674, these two pieces of patents mode by reference is incorporated to this paper.
Described many (sulfuryl azide) is for having at least two sulfuryl azide group (that is ,-SO that can react with the ethylene/alpha-olefin interpolymers that the application discloses 2n 3) any compound.In some embodiments, described many (sulfuryl azides) have the structure of X-R-X, and wherein each X is-SO 2n 3and R means alkyl, hydrocarbyl ether or silicon-containing group unsubstituted or that inertia replaces.In some embodiments; described R group has enough carbon atoms, Sauerstoffatom or Siliciumatom; be preferably carbon atom, fully to separate the sulfuryl azide group, to allow easily reaction between ethylene/alpha-olefin interpolymers and sulfuryl azide group.In other embodiments, described R group has at least 1 between the sulfuryl azide group, and at least 2, or at least 3 carbon atoms, Sauerstoffatom or Siliciumatoms, be preferably carbon atom.Term " inertia replaces " refers to atom or the reaction of one or more hope that group can hopefully hinder the gained cross-linked polymer or the character of hope of replacement.This group comprises fluorine, aliphatic series or aromatic oxide, siloxanes etc.The limiting examples of the applicable structure of R comprises aryl, alkyl, alkaryl, aralkyl, silylation, heterocyclic radical and other inertia group.In some embodiments, described R group comprises at least one aromatic group between alkylsulfonyl.In other embodiments, described R group comprise at least two aromatic yl groups (for example when R be 4,4 '-phenyl ether or 4,4 '-during biphenyl).When R is an aromatic yl group, preferably, described group has the ring of surpassing, in the situation at naphthalene two (sulfuryl azide).In some embodiments, described many (alkylsulfonyl) trinitride comprises 1, 5-pentane two (sulfuryl azide), 1, 8-octane two (sulfuryl azide), 1, 10-decane two (sulfuryl azide), 1, 10-octodecane two (sulfuryl azide), 1-octyl group-2, 4, 6-benzene three (sulfuryl azide), 4, 4 '-phenyl ether two (sulfuryl azide), 1, 6-bis-(4 '-the sulfonyl azide base groups phenyl) hexane, 2, 7-naphthalene two (sulfuryl azide) and each molecule on average contain the sulfuryl azide of mixing of the chlorination aliphatic hydrocrbon of 1-8 chlorine atom and about 2-5 sulfuryl azide group, and combination.In other embodiments; described many (sulfuryl azide) comprises oxygen connection-bis-(4-alkylsulfonyl triazobenzenes), 2; 7-naphthalene two (alkylsulfonyl azido-), 4; 4 '-bis-(alkylsulfonyl azido-) biphenyl, 4; 4 '-phenyl ether two (sulfuryl azide) and two (4-alkylsulfonyl azido-phenyl) methane, and combination.
The limiting examples of applicable aldehyde-amine reaction product comprises formaldehyde-ammonia, formaldehyde-ethyl chloride-ammonia, acetaldehyde-ammonia, formaldehyde-aniline, butyraldehyde-aniline, enanthaldehyde-aniline and combination thereof.
The limiting examples of the urea of applicable replacement comprises trimethyl thiourea, diethyl thiourea, dibutyl thiourea, three amyl group thiocarbamides, 1,3-bis-(2-[4-morpholinodithio base sulfenyl methyl) urea, N, N-diphenyl thiourea and combination thereof.
The limiting examples of the guanidine of applicable replacement comprises two of diphenylguanidine, two-o-tolyl guanidine, phthalic acid diphenylguanidine, boric acid two catechu phenolic esters-o-tolyl guanidinesalt and combination thereof.
The limiting examples of the xanthate of applicable replacement comprises zinc ethyl xanthate, Good-Rite Nix, butyl xanthyl disulphide (butylxanthic disulfide), potassium isopropyl xanthate, zinc butyl xanthate and combination thereof.
The limiting examples of applicable dithiocar-bamate comprises cupric dimethyldithiocarbamate, ziram, tellurium diethyl dithiocarbamate, dicyclohexyl dithiocarbamic acid cadmium, lead dimethyl dithiocarbamate, lead dimethyl dithiocarbamate, selenium dibutyldithiocarbamate, zinc pentamethylene dithiocarbamate, didecyl zinc dithiocarbamate, sec.-propyl octyl group zinc dithiocarbamate and combination thereof.
The limiting examples of applicable thiazole comprises 2-mercaptobenzothiazole, thyroidan base sulphur zinc alcoholate (zinc mercaptothiazolyl mercaptide), 2-[4-morpholinodithio base-N; N-diethyl thiocarbamoyl sulfide, 2,2 '-dithio two (benzothiazole) and combination thereof.
The limiting examples of applicable imidazoles comprises 2-mercaptoimidazoline, 2-sulfydryl-4,4,6-trimethylammonium dihydro-pyrimidin, and combination.
The limiting examples of applicable sulfinyl amine comprise N-tert-butyl-2-[4-morpholinodithio-, N-cyclohexyl benzo thiazole-, N, N-di-isopropyl benzo thiazole-, N-(2,6-thebaine generation)-2-[4-morpholinodithio-, N, N-diethyl benzo thiazole-sulfinyl amine and combination thereof.
The limiting examples of applicable thiuram-disulfide comprises N, N '-diethyl-, the tetrabutyl-, N, N '-di-isopropyl dioctyl-, tetramethyl--, N, N '-dicyclohexyl-, N, N '-tetra-lauryl thiuram-disulfide and combination thereof.
In some embodiments, described linking agent is silane.The ethylene/alpha-olefin interpolymers that can use the ethylene/alpha-olefin interpolymers that can be effectively discloses with the application or blend polymer grafting and/or crosslinked the application to disclose or any silane of blend polymer.The limiting examples of applicable silane crosslinker comprises undersaturated silane; it comprises the undersaturated alkyl of ethylenic as vinyl, allyl group, pseudoallyl, butenyl, cyclohexenyl or γ-(methyl) acryloxy allyl group, and hydrolysable group is as-oxyl (hydrocarbyloxy), carbonic acyl radical oxygen base (hydrocarbonyloxy) and alkyl amino.The limiting examples of applicable hydrolysable group comprises methoxyl group, oxyethyl group, methanoyl, acetoxyl group, propionyloxy (proprionyloxy), alkyl and arylamino.In other embodiments, described silane be can grafting on interpretation undersaturated organoalkoxysilane.Some in these silane and their preparation method are described in United States Patent (USP) 5,266 more fully, and in 627, by it, mode by reference is incorporated to this paper.In other embodiments, described silane crosslinker is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyltriacetoxy silane, vinyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane and combination thereof.
Depend on the amount of silane, processing conditions, the grafting initiator of person's character, the use of ethylene/alpha-olefin interpolymers or blend polymer, finally application and other factors, the amount of silane crosslinker can change widely.When using vinyltrimethoxy silane (VTMOS), the amount of VTMOS is generally at least about 0.1 % by weight, at least about 0.5 % by weight, or at least about 1 % by weight, the combination weight based on silane crosslinker and interpretation or blend polymer.
Purposes
Described embodiment vinyl-type polymer can be used in multiple conventional fabrication methods for thermoplastics, to manufacture useful goods, described goods comprise that the article that comprise at least one rete are as unitary film, or at least one layer in the multilayer film prepared by curtain coating, blowing, calendering or extrusion coating method; Moulded product, for example blow-molded article, injection-molded item or rotation molded articles; Extruded product; Fiber; With woven cloths or non-woven.The thermoplastic compounds that comprises the embodiment vinyl-type polymer comprises blend natural with other or synthetic materials, polymkeric substance, additive, toughener, flame-retardant additive, antioxidant, stablizer, tinting material, extender, linking agent, whipping agent and softening agent.
For other application, described embodiment vinyl-type polymer can be used for manufacturing fiber.The fiber that can be prepared by embodiment vinyl-type polymer or its blend comprises staple fibre (staple fibers), fibrous bundle (tow), multicomponent fibre, skin/core fibre, twisted fibers and monfil.Applicable fiber formation method comprises United States Patent (USP) 4, 340, 563 (people such as Appel), 4, 663, 220 (people such as Wisneski), 4, 668, 566 (people such as Nohr) and 4, 322, spunbond and melt blown technology disclosed in 027 (Reba), United States Patent (USP) 4, 413, the gel staple fiber (gel spun fibers) disclosed in 110 people such as () Kavesh, United States Patent (USP) 3, 485, the woven cloths and the non-woven that in 706 (May), disclose, perhaps by this fiber, (comprised with other fiber as polyester, the blend of nylon or cotton) structure of manufacturing, articles thermoformed therefrom, extruded profile (comprising special-shaped extrudate and coextrusion thing), calendered goods and stretching, twisting or curling yarn or fiber.
Described embodiment vinyl-type polymer can be used in multiple film, and described film includes but not limited to transparent shrink film, collation shrink film, casting and stretching film, silage film, stretching buncher film (stretch hooder films), sealing agent (sealants), durable bags film (stand up pouch films), lining form and diaper back sheet material.
Described embodiment vinyl-type polymer also can be used for other direct end-use application.Described embodiment vinyl-type polymer can be used for electric wire and cable coating operation, operates for vacuum forming in sheet material is extruded, and is used to form moulded product (comprising injection moulding, blow moulding or the rotational moulding method used).The composition that also can use conventional polyolefine processing technology will comprise described embodiment vinyl-type polymer is configured as goods.
Other applicable application of described embodiment vinyl-type polymer comprises film and fiber; Soft tactile commodity, for example toothbrush handle and device handle (appliance handles); Liner (gaskets) and section bar (profiles); Tackiness agent (comprising hotmelt and pressure sensitive adhesive); Footwear (comprising sole and sock); Automobile inner part and section bar (auto interior parts and profiles); Foams commodity (perforate with closed pore); Other thermoplastic polymer is as the impact modifier of high density polyethylene(HDPE), isotactic polyprophlene or other olefin polymer; Adhesive plaster (coated fabrics); Sebific duct (hoses); Tubing (tubing); Weather strip (weather stripping); Lid lining (cap liners); Flooring material (flooring); And VI improver, also referred to as pour point properties-correcting agent, for lubricant.
Can to described embodiment vinyl-type polymer be further processed with by described embodiment vinyl-type polymer for other end-use.The preparation that for example, also can use polymkeric substance of the present invention or comprise polymkeric substance of the present invention forms dispersion (water-based with nonaqueous).Also can form the foams (frothed foams) of the foaming that comprises described embodiment vinyl-type polymer, disclosed in text 2005/021622 as open as PCT people such as () Strandburg.Described embodiment vinyl-type polymer also can be crosslinked by any known way, for example uses superoxide, electron beam, silane, trinitride or other crosslinking technological.Also can be by described embodiment vinyl-type polymer chemical modification, for example, by grafting (for example, by using maleic anhydride (MAH), silane or other grafting agent), halogenation, amination, sulfonation or other chemical modification.
Can add additive and auxiliary to the embodiment membrane structure.Applicable additive comprises filler, for example the organic or inorganic particle, comprise clay, talcum, titanium dioxide, zeolite, powder metal, the organic or inorganic fiber, comprise carbon fiber, silicon nitride fiber, steel wire or steel mesh, and nylon or polyester rope, nano size particles, clay etc.; Tackifier, oil extender (oil extenders), comprise paraffin oil or naphthenic oil (napthelenic oils); And other natural and synthetic polymkeric substance, comprise other polymkeric substance prepared according to method embodiment or other polymkeric substance that can prepare according to method embodiment.
Can be by described embodiment vinyl-type polymer with other polyolefin blend with mix.For with the applicable polymkeric substance of described embodiment vinyl-type polymer blend, comprising thermoplasticity and non-thermal plasticity polymkeric substance (comprising natural and synthetic polymer).Illustrative polymers for blend is drawn together polypropylene (impact-resistant modified polypropylene, isotactic polyprophlene, atactic polypropylene(APP) and random ethylene/propylene multipolymer), various types of polyethylene, comprise high-pressure free radical LDPE, Z-N LLDPE, metallocenes PE, comprise multiple reactor PE (" in reactor (in reactor) " blend of Z-N PE and metallocenes PE, for example, at United States Patent (USP) 6,545,088 (people such as Kolthammer); 6,538,070 (people such as Cardwell); 6,566,446 (people such as Parikh); 5,844,045 (people such as Kolthammer); 5,869,575 (people such as Kolthammer); With 6,448, the product disclosed in 341 people such as () Kolthammer), ethane-acetic acid ethyenyl ester (EVA), ethylene/vinyl alcohol copolymer, polystyrene, impact-resistant modified polystyrene, ABS, styrene/butadiene block copolymer and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethane.Homopolymer (for example, can be by trade(brand)name VERSIFY as alkene plastomer and elastomerics, multipolymer based on ethene and propylene tMplastomers & Elastomers (The Dow Chemical Company) and VISTAMAXX tMthe polymkeric substance that (ExxonMobil Chemical Co.) obtains) component in the blend that also can be used as comprising described embodiment vinyl-type polymer.
The blend of described embodiment vinyl-type polymer and mixture can comprise thermoplastic polyolefin blend (TPO), thermoplastic elastomer blend (TPE), Thermoplastic Vulcanizate (TPV) and styrenic polymer blend.Can prepare by TPE and TPV blend: make embodiment vinyl-type polymer (comprising its functionalized or undersaturated derivative) and optional rubber (comprising conventional segmented copolymer, is especially the SBS segmented copolymer) and optional linking agent or vulcanizing agent mixing by the following method.The TPO blend is preparation by the following method usually: embodiment polymkeric substance and polyolefine and optional linking agent or vulcanizing agent are mixed.Aforementioned blend can form moulded product and optionally use in crosslinked gained moulded product.Use the similar operations of different components at United States Patent (USP) 6,797, formerly disclose in 779 people such as () Ajbani.
Definition
The term " composition " used comprises the material that forms composition and the reaction product formed by the material of composition and the mixture of degradation production.
The homogeneous physical mixture (that is, reactionless) that the term " blend " used or " blend polymer " refer to two or more polymkeric substance.Blend solvable mixed (not being separated at molecular level) or can be non-miscible.Blend can be separated or can not be separated.Blend can contain or can not contain one or more microcell configurations (domain configurations), as measured by transmitted electron spectroscopy, scattering of light, x-ray scattering and other method known in the art.Blend can be by for example, for example, at macroscopic scale (, melt blending resin or be mixed) or upper two or more polymkeric substance of physical mixed of microscopic scale (, forming in same reactor) simultaneously and form.
Term " linearity " refers to that main polymer chain lacks measurable or demonstrable long chain branches, and for example, for every 1000 carbon, polymkeric substance on average replaces and is less than 0.01 long branch.
Term " polymkeric substance " refers to the polymerizable compound prepared by polymerization single polymerization monomer (no matter being same type, still dissimilar).Therefore, the general terms polymkeric substance comprises the term " interpretation " of term " homopolymer " (being generally used for meaning the polymkeric substance only prepared by a kind of monomer) and definition.Term " ethylene/alpha-olefin polymer " shows as described interpretation.
Term " interpretation " refers to the polymkeric substance prepared by least two kinds of dissimilar monomers of polymerization.The general terms interpretation comprises multipolymer (be generally used for mean prepared by two kinds of different monomers polymkeric substance) and by surpassing two kinds of polymkeric substance prepared by dissimilar monomer.
Term " polymkeric substance based on ethene " refers to such polymkeric substance: it contains the polymerizing ethylene monomer (total amount based on polymerisable monomer) that surpasses 50 % by mole, and optionally, can contain at least one comonomer.
Term " ethylene/alpha-olefin interpolymers " refers to and contains the interpretation that surpasses 50 % by mole of polymerizing ethylene monomer (total amount based on polymerisable monomer) and at least one alpha-olefin.
Term " vinyl-type polymer " refers to by the polymkeric substance based on ethene and at least one polymkeric substance that highly bonding of the polymkeric substance based on ethene of long chain branching causes.
Test method
Density
Density (g/cm 3) according to ASTM-D 792-03, method B measures in Virahol.In molded one hour, adapt to 8 minutes before measuring, to realize thermal equilibrium in the isopropanol bath of 23 ℃.Sample is according to ASTM D-4703-00 appendix A, with in approximately 5 minutes initial heating time of 190 ℃ and the speed of cooling of 15 ℃/min, according to program C compression moulding.Sample is cooled to 45 ℃ in press, and continues cooling until " touching and feeling cool ".
Melt index
Melt index or I 2according to ASTM D 1238,190 ℃/2.16kg of condition measures, and reports with the grams of outflow in every 10 minutes.I 10according to ASTM D 1238,190 ℃/10kg of condition measures, and reports with the grams of outflow in every 10 minutes.
DSC degree of crystallinity
Can use dsc (DSC) to measure melting and the crystallization behavior of going through the wide temperature range polymkeric substance.For example, use the TA Instruments Q1000 DSC that is furnished with RCS (refrigerating/cooling system) and self-actuated sampler to implement this analysis.At test period, use the nitrogen sweeping gas flow velocity of 50ml/min.Each sample is pressed into to film in about 175 ℃ of meltings; Then by the fusing sample air cooling to room temperature (approximately 25 ℃).By 3-10mg, the sample of 6mm diameter takes out from cooling polymkeric substance, weighs, and be placed in lightweight aluminium dish (about 50mg), and (crimped shut) is closed in crimping.Then implement to analyze to measure thermal properties.
By improving and reduce the thermal behavior of sample temperature working sample, to produce the curve of hot-fluid to temperature.At first, sample is heated to rapidly to 180 ℃ and constant temperature and keeps 3 minutes, to remove its thermal history.Then, sample is cooled to-40 ℃ and keep 3 minutes at-40 ℃ of constant temperature with 10 ℃ of/minute rate of cooling.Then sample is heated to 150 ℃ (these are " the second heating " oblique lines) with the heating rate of 10 ℃/minute.Record cooling and the second heating curve.Cooling curve is analyzed by the following method: from crystallization, start to set the baseline end points to-20 ℃.Heating curve is analyzed by the following method: from-20 ℃ to melting end setup baseline end points.The value of measuring is peak melt temperature (T m), peak Tc (T c), melting heat (H f) (in joule/gram), and the crystallinity percentage of the polyethylene specimen of using following formula to calculate:
Crystallinity percentage=((H f)/(292J/g)) x100.
From the second heating curve report melting heat (H f) and the peak melt temperature.Measure the peak Tc from cooling curve.
Gel permeation chromatography (GPC)
The GPC system is by being furnished with built-in differential refractometer (on-board differential refractometer) Waters (Milford (RI), MA) 150C high temperature chromatographic instrument (other applicable high temperature GPC instrument comprises Polymer Laboratories (Shropshire, UK) Model 210 and Model 220) forms.Other detector can comprise Polymer ChAR (Valencia, Spain) IR4 infrared detector, Precision Detectors (Amherst, MA) 2-angle laser light scattering detector Model 2040 and Viscotek (Houston, TX) 150R 4-kapillary soltion viscosity meter.GPC with latter two individual detectors and at least one first detector is called as " 3D-GPC " sometimes, and independent term " GPC " typically refers to conventional GPC.Depend on sample, the 15-degree angle of light scattering detector or 90-degree angle are used for calculating purpose.Data gathering is used Viscotek TriSEC software the 3rd edition and 4-passage Viscotek Data Manager DM400 to carry out.Described system also is furnished with the online solvent degassing equipment of Polymer Laboratories (Shropshire, UK).Can use applicable high temperature GPC post, for example four 13 microns posts of the long Shodex HT803 of 30cm or four 30cmPolymer Labs posts (MixA L S, Polymer Labs) with 20-micron mixing porosity filler.Sample spin chamber (sample carousel compartment) 140 ℃ the operation and column compartment 150 ℃ of operations.Prepared with following concentration by sample: 0.1 gram polymkeric substance in 50 milliliters of solvents.The Yoshinox BHT that chromatographic solvent and sample preparation solvent contain 200ppm (BHT).With two kinds of solvents of nitrogen jet.By polyethylene specimen 160 ℃ of gentle stirrings 4 hours.Spraying volume is 200 microlitres.Flow velocity by GPC is made as 1ml/ minute.
Calibrated GPC post groups by 21 narrow molecular weight distributions polystyrene standards of operation before operation embodiment.The molecular weight of standard substance (MW) is 580-8,400,000 g/mols, and standard substance is included in 6 " cocktail (cocktail) " mixtures.Each standard mixture has the interval of at least ten times between each molecular weight.Standard mixture is purchased from Polymer Laboratories (Shropshire, UK).Be equal to or greater than 1,000,000g/mol for molecular weight, with the standby polystyrene standards of 0.025 restraint in 50 milliliters of solvents, for molecular weight, be less than 1,000,000g/mol, with the standby polystyrene standards of 0.05 restraint in 50 milliliters of solvents.Relax to stir at 80 ℃ and polystyrene standards was dissolved in 30 minutes.The order of at first successively decreasing with the highest weight component is moved narrow standard substance mixture, so that minimum degradation.Use the described Mark-Houwink K of following p-poly-phenyl ethene and polyethylene and a (being sometimes referred to as α) value that polystyrene standards peak molecular weight is changed into to polyethylene M w.Referring to the embodiment part of proving this program.
For 3D-GPC, use aforesaid the same terms, absolute weight molecular-weight average (" M w, Abs ") and intrinsic viscosity also independently derive from applicable narrow polyethylene standard thing.These narrow linear polyethylene standard substances can derive from Polymer Laboratories (Shropshire, UK; Part No. ' s PL2650-0101 and PL2650-0102).
The systems approach of measuring multi-detector deviation (multi-detector offsets) by with Balke, the people such as Mourey (Mourey and Balke, Chromatography Polym. the 12nd chapter, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. the 13rd chapter, (1992) mode that) disclosed mode is consistent is implemented, thereby will be from the wide polystyrene of Dow 1683 (American Polymer Standards Corp.; Mentor, OH) or three detector logarithms (triple detector the log) (M of its Equivalent wwith intrinsic viscosity) result optimizing becomes the narrow standard column calibration result from narrow polystyrene standards working curve.Consider the detector volume deviation measuring, molecular weight data (Zimm with Zimm, B.H., J.Chem.Phys., 16,1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)) mode that disclosed mode is consistent obtains.The total implantation concentration used in molecular weight determination derives from mass detector area and mass detector constant, and described mass detector constant is derived from applicable linear polyethylene homopolymer or a kind of polyethylene standard thing.Use obtains derived from the Light Scattering of one or more described polyethylene standard things and 0.104 specific refractory power concentration factor dn/dc the molecular weight calculated.Usually, mass detector response and Light Scattering should surpass approximately 50,000 daltonian linear criterion things mensuration from molecular weight.Viscometer calibration can use the described method of manufacturers or selectively by use applicable linear criterion thing as standard reference material (Standard Reference Materials) (SRM) 1475a, 1482a, 1483 or the disclosed value of 1484a complete.Suppose that chromatographic concentrations is enough low, with Processing for removing second virial coefficient effect (molecular weight concentration effect).
Analytical temperature rising elution classification (ATREF):
High-density fraction (percentage ratio) property temperature rising elution hierarchical analysis (ATREF) is by analysis measured.ATREF analyzes according at United States Patent (USP) 4,798, and 081 and Wilde, L.; RyIe, T.R.; Knobeloch, D.C; Peat, LR.; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, Journal of Polymer Science, the method for describing in 20,441-455 (1982) is carried out.The composition dissolves analyzed, in trichlorobenzene, and is made to its crystallization in containing the post of inert support (stainless shot) by the rate of cooling slow cooling to 20 ℃ with 0.1 ℃/min.Described post is furnished with infrared detector.Then produce by the following method the ATREF chromatographic curve: by the speed with 1.5 ℃/min, eluting solvent (trichlorobenzene) temperature slowly is increased to 120 ℃ from 20 ℃, from described post wash-out crystalline polymer sample.Measure and report the viscosity-average molecular weight (Mv) of wash-out polymkeric substance.The ATREF collection of illustrative plates has short-chain branched distribution (SCBD) collection of illustrative plates and molecular weight collection of illustrative plates.The SCBD collection of illustrative plates has 3 peaks, and one means high crystalline fraction (usually above 90 ℃), and one means multipolymer fraction (being generally 30-90 ℃) and an expression flushing fraction (being usually less than 30 ℃).Curve also has paddy between multipolymer fraction and high crystalline fraction.Thc is the minimum temperature in paddy.High-density (LTD) fraction percentage ratio is the area under a curve higher than Thc.Mv is the viscosity-average molecular weight from ATREF.Mhc is the average Mv higher than the fraction of Thc.Mc is the average Mv of the multipolymer between 60 ℃ to 90 ℃.Mp is the average Mv of whole polymkeric substance.
Drip washing classification (F-TREF) is rapidly heated
Fast-TREF can use Polymer ChAR (Valencia, Spain) Crystex instrument, in orthodichlorobenzene (ODCB), IR-4 infrared detector (Polymer ChAR by compositional model, Spain) and scattering of light (LS) detector (Precision Detector Inc., Amherst, MA) implement.
When test F-TREF, the 120mg sample is added in the Crystex reactor vessel with 40ml ODCB, at 160 ℃, keep 60 minutes, the while mechanical stirring, to realize sample dissolution.Sample is loaded on the TREF post.Then cooling sample solution in two stages: (1) with 40 ℃/minute from 160 ℃ to 100 ℃, and (2) polymer crystallization process, with 0.4 ℃/minute from 100 ℃ to 30 ℃.Then, sample solution is kept 30 minutes at 30 ℃ of constant temperature.The intensification elution process is with 1.5 ℃/minute from 30 ℃ to 160 ℃, and flow velocity is 0.6ml/ minute.The sample loaded volume is 0.8ml.Molecular weight analyte (Mw) is calculated as to 15 ° or the 90 ° of LS signals ratio with respect to the signal from IR-4 detector measures sensor.The LS-MW calibration constants obtains by the polyethylene whole nation office (polyethylene national bureau) of Application standard thing SRM 1484a.Eluting temperature is reported as to actual furnace temperature.Considered that in the TREF eluting temperature of report the tubulature between TREF and detector postpones volume (tubing delay volume).
Preparative temperature rising elution classification (P-TREF)
Temperature rising elution stage division (TREF) can be used for preparation property ground classification polymkeric substance (P-TREF) and derived from Wilde, L.; RyIe, T.R.; Knobeloch, D.C.; Peat, I.R.; " Determination ofBranching Distributions in Polyethylene and Ethylene Copolymers ", J.Polym.ScL, 20,441-455 (1982), comprise column dimension, solvent, flow velocity and temperature planning.Use the wash-out of infrared (IR) absorption detector monitoring polymer from post.Also used the liquid bath of independent planning temperature, one loads for post, and one for the post wash-out.
Prepared by the following method by sample: be dissolved in containing approximately 0.5%2 at 160 ℃, in the trichlorobenzene of 6-bis--tert-butyl-4-methyl-Phenol (TCB), provide stirring with magnetic stirring bar simultaneously.Sample load is the about 150mg of every post.After 125 ℃ of loadings, last approximately 72 hours, post and sample are cooled to 25 ℃.Then but cooling sample and post are transferred to the bath of the second temperature programmed control and keep balance at 25 ℃ of TCB with 4ml/ minute constant rate.Start the linear temperature program, so that temperature is with approximately 0.33 ℃ of/minute rising, approximately reaching the top temperature of 102 ℃ in 4 hours.
Place the manual fraction of collecting of receiving flask by the exit at the IR detector.ATREF based on early analyzes, and collects the first fraction from 56 ℃ to 60 ℃.Collect little fraction (being called subfraction) subsequently, every 4 ℃ until 92 ℃, then every 2 ℃ until 102 ℃.Subfraction means by the mid point eluting temperature (midpoint elution temperature) of collecting subfraction.
Often the scope by neutral temperature is gathered into larger fraction by subfraction, to be tested.Purpose for test, can further be combined into larger fraction by fraction.
The mean value of the eluting temperature scope based on each subfraction and subfraction weight, to the sample gross weight, are measured the weighted average eluting temperature of each fraction.The weighted average temperature is defined as:
T w = &Sigma; T T ( f ) * A ( f ) / &Sigma; T A ( f )
Neutral temperature and A (f) that wherein T (f) is narrow part or fragment are the area of fragment, proportional with the amount of polymkeric substance in fragment.
EXCEL (Microsoft Corp. is stored and used to data with digital form; Redmond, WA) the electronic data list processing.Calculate TREF collection of illustrative plates, peak top temperature, fraction weight percentage and fraction weighted average temperature with spreadsheet program.
Mist degree is measured according to ASTM-D 1003.
45 ° of glossiness are measured according to ASTM-2457.
Elmendorf cracking resistance power is measured according to ASTM-D 1922.
Modulus and tension test are measured according to ASTM D 882.
Dart impact intensity is according to ASTM-D 1709-04, and method B measures.
The C13NMR co-monomer content
It is known using NMR spectrographic determination polymer composition.People (" NMR and Macromolecules " the ACS Symposium series 247 such as ASTM D 5017-96, J.C.Randall, J.C.Randall, Ed., Am.Chem.Soc, Washington, D.C., 1984, Ch.9) and J.C.Randall (" Polymer Sequence Determination ", Academic Press, New York (1977)) general method that carries out polymer analysis by NMR spectrum is provided.
Gel content is measured
At least part of when crosslinked when ethene interpretation (independent or be contained in composition), degree of crosslinking can be measured by the following method: composition dissolves is reached in solvent to the fixed time, and calculated for gel or percentage ratio that can not extraction components.Gel fraction increases with crosslinked level usually.For cured article according to the present invention, gel content percentage ratio is desirably at least about 5% to 100%, according to ASTM D-2765, measures.
Embodiment
The preparation of the polymkeric substance based on ethene
Multicomponent catalyst
Exemplary multi-component catalyst systems comprises Ziegler-Natta catalyst composition (comprising procatalyst and promotor containing magnesium and titanium).Described procatalyst is for carrying the MgCl of titanium 2ziegler Natta catalyzer is characterised in that Mg: the Ti mol ratio is 40: 1.0.Described promotor is triethyl aluminum.The Ti of described procatalyst: the Mg ratio can be 1.0: 40-5.0: 40, be preferably 3.0: 40.Can before entering reactor or in reactor, contact described procatalyst and cocatalyst component.Described procatalyst can be for example any other Ziegler Natta catalyzer based on titanium.The Al of cocatalyst component to the procatalyst component: the Ti mol ratio can be approximately 1: 1 to approximately 5: 1.
The general description of multi-component catalyst systems
Multi-component catalyst systems used in this application refers to Ziegler-Natta catalyst composition (comprising procatalyst and promotor containing magnesium and titanium).Described procatalyst can for example comprise the reaction product of magnesium dichloride, dihalide aluminum alkyls and alkyl dioxide.
The olefin polymerization procatalyst precursor comprises the product obtained by the following method: mix
(A) magnesium halide prepared by the following method: (1) is contacted with (2),
(1) the soluble magnesium component of at least one hydrocarbon, be expressed as general formula R " R ' Mg.xAlR ' 3, wherein each R " and R ' be alkyl;
(2) at least one halide source nonmetal or metal, under such condition: make temperature of reaction be no more than approximately 60 ℃, preferably be no more than approximately 40 ℃, and be most preferably not exceeding approximately 35 ℃;
(B) at least one transistion metal compound, be expressed as formula Tm (OR) y Xy-x, the metal of IVB, VB, VIB, VIIB or VIII family that wherein Tm is the periodic table of elements; R is for having 1 to approximately 20, and preferably 1 to the about alkyl of 10 carbon atoms;
(C) other halide source, if the quantity not sufficient of the component (A-2) existed is to provide the excessive X of hope: the Mg ratio.
Particularly suitable transistion metal compound comprises, for example, titanium tetrachloride, titanous chloride, vanadium tetrachloride, zirconium tetrachloride, four (isopropoxy) titanium, four titanium butoxide, diethoxy dibrominated titanium, dibutoxy titanium dichloride, four phenoxide titaniums, three isopropoxy vanadium oxides, four n-propoxyzirconium and composition thereof etc.
Other applicable titanium compound that can use as transition metal component in this application comprises titanium complex and/or the compound obtained by the following method: (A) reacted with (B),
(A) at least one titanium compound, be expressed as formula Ti (OR) x X4-x, and wherein each R is alkyl independently, and described alkyl has 1 to approximately 20, and preferably approximately 1 to approximately 10, most preferably from about 2 to about 4 carbon atoms; X is the value that halogen and x have 0-4;
(B) at least one is containing the compound of at least one aromatic hydroxy.
By aforementioned procatalyst component to be enough to the providing ratio of aforementioned atom ratio to be combined.
Preferably, prepared by aforementioned procatalyst reaction product under the existence of inert diluent.The concentration of catalyst component preferably makes when the basal component of assembly catalyze reaction product, and the magnesium of gained slurry is approximately 0.005 to about 1.0 volumetric molar concentrations (molar) (mol/L).For example, applicable inertia organic thinner can be liquefaction ethane, propane, Trimethylmethane, normal butane, normal hexane, various isomery hexane, octane-iso, there is paraffinic mixture, hexanaphthene, methylcyclopentane, dimethyl cyclohexane, dodecane, the industrial solvent of the alkane of 8-12 carbon atom, its hydrocarbon that comprises saturated or aromatics is as kerosene, petroleum naphtha etc., especially when not containing any olefin(e) compound and other impurity, and especially boiling point be approximately-50 ℃ of extremely approximately those of 200 ℃.Mix described procatalyst component with catalytic reaction products that hope is provided advantageously inert atmosphere as nitrogen, argon gas or other rare gas element under, at approximately-100 ℃ to approximately 200 ℃, preferably approximately-20 ℃ of extremely approximately temperature of 100 ℃ preparations, condition is: prepare magnesium halide carrier, make temperature of reaction be no more than approximately 60 ℃.In the preparation of catalytic reaction products, needn't make the hydrocarbon soluble constituent separate with the hydrocarbon indissolvable component of reaction product.
Described procatalyst compositions, as a component of Ziegler-Natta catalyst composition, combines with promotor.Preferably, the molar ratio of the titanium based in described procatalyst of the promotor of use is 1: 1-100: 1, but more preferably 1: 1-5: 1.
Resin embodiment 1 of the present invention
According to following operation, prepared by resin embodiment 1 of the present invention: prepared by non-homogeneous branching ethylene/alpha-olefin copolymer by the following method: use the above-mentioned multi-component catalyst systems that is suitable for making ethene and one or more alpha-olefin comonomer (for example 1-octene) (being total to) polymerization, in two that are connected in series adiabatic ball reactors, under solution condition, operate.For example, by vinyl monomer, 1-octene copolymer monomer and hydrogen and solvent,
Figure BDA0000114323310000231
e, can be purchased from ExxonMobil.By feedstream from polar impurity as water, carbon monoxide, sulphur compound and unsaturated compound as the acetylene purifying and be cooled to 13 ℃ before entering reactor.Most of (85-90%) reaction occurs in the first ball reactor of 10 ft diams.Mixing realizes through following methods: with the agitator circulating polymerization thing/catalyst/co-catalyst of being furnished with agitating vane/solvent/ethylene/comonomer/hydrogen solution.Feed (ethene/comonomer/solvent/hydrogen) enters reactor and catalyst/co-catalyst to be separated with feed and also from bottom, enters reactor from bottom.The first temperature of reaction is approximately 175 ℃, and reactor pressure is about 500psi.Rise to 202 ℃ with the temperature of the second reactor of the first reactors in series, the residue reaction of about 10-15% occurs and do not add other stream.Catalyst/co-catalyst Al/Ti volumetric molar concentration feed ratio is made as 1.5.Before stopping be used for the fluid reactor stopped by specialized designs after, the average reactor residence time is each ball reactor approximately 8 minutes.After polymers soln leaves reactor, solvent is removed from polymers soln with unconverted vinyl monomer through secondary devolatilizer system together with 1-octene copolymer monomer, then reclaim.Before again entering reactor, purifying reclaims stream.The polymer melt pump is crossed to the die head of specialized designs for granulation underwater.Pellet is transferred to sizing screen to remove excessive and too small particle.Then the pellet completed is transferred to railcar.The character of non-homogeneous branching ethylene/alpha-olefin copolymer is listed in table 1.The ATREF that Fig. 1 is resin embodiment 1 of the present invention.
The co-extruded films that comprises the first ethylene/alpha-olefin copolymer (co-ex film) has further processing on the Reifenhauser blown film production line of 250mm diameter die head through trapped-air process.Described die head has the gap of 2.59mm.Described film is with the blow-up ratio of approximately 2.2: 1 and the approximately frost line height blowing of 30 inches.The width that keeps flat of film is about 880mm, and the thickness of film is listed in table 3 simultaneously.3 layers of coextrusion resin melting are extruded by annular circular die (annular circular die).Hot melts occurs from die head, forms thus pipe.Described pipe is by air expansion, and simultaneously, cooling air becomes solid-state by thin slice (web) chilling.Then, the film pipe caves in (collapse) and clamps in the end of framework in the V-of roller gap frame C, with by air entrapment in film bubble.Described nip rolls is the tractive film also, makes it away from die head.Described pipe is cut and is wrapped on roller as single rete.The character of comparative film and film of the present invention is listed in table 3.
Resin comparative examples 1
Resin comparative examples 1 (linear low density polyethylene) is with 190 ℃ of temperature of reaction and 3.5: the preparation of 1Al/Ti ratio.All other conditions are identical with the embodiment of the present invention 1.The character of Comparative Examples 1 is listed in table 1.The ATREF that Fig. 1 is Comparative Examples 1.Comparative Examples 1 is processed through above-mentioned trapped-air process.Comparative Examples 1 is melt extruded by annular circular die.Hot melts occurs from die head, forms thus pipe.Described pipe is by air expansion, and simultaneously, cooling air becomes solid-state by the thin slice chilling.Then, the film pipe caves in and clamps in the end of framework in the V-of roller gap frame C, with by air entrapment in film bubble.Described nip rolls is the tractive film also, makes it away from die head.Described pipe is cut and is wrapped on roller as single rete.The character of comparative film 1 is listed in table 2.
Table 1: resin manufacture and the characterization data of resin 1 of the present invention and Comparative Examples 1.
Describe The embodiment of the present invention 1 Comparative Examples 1
Resin M I (g/10 minute) 0.80 0.80
Resin density (g/cc) 0.917 0.917
Catalyzer HEC-3 HEC-3
Fi/40Mg 3 3
Al/Ti 1.5 3.5
Rx. temperature (℃) 175 190
M hc 103000 143000
M c 64234 54815
M p 76542 71007
M hc/M p 1.35 2.01
M c/M p 0.84 0.77
HD level part percentage ratio-ATREF 10.6 15.4
T hc, the minimum temperature in the paddy between multipolymer and high crystalline fraction
M v, from the viscosity-average molecular weight of ATREF
M hc, from ATREF higher than T hcthe average M of fraction v
M c, the average M of the multipolymer between 60-90 ℃ v-ATREF
M p, from the average M of the block polymer of ATREF v
HD fraction percentage ratio, higher than T hcarea under a curve
Table 2: the character of the film prepared by resin 1 of the present invention and Comparative Examples 1
Figure BDA0000114323310000251
Comparative resin 2: the LLDPE based on octene prepared by solution method and Z-N catalyzer.I 2(190℃.2.16KG)：1g/10min。Density: 0.920g/cm 3;
Comparative resin 3: the LLDPE based on octene prepared by solution method and Z-N catalyzer.I 2(190℃.2.16KG)：1g/10min。Density: 0.935g/cm 3;
Resin 2 of the present invention: the LLDPE based on octene prepared by solution method with as the improved Z-N catalyzer in resin 1 of the present invention, I 2(190 ℃ of .2.16KG): 0.5g/10min.Density: 0.917g/cm 3;
Comparative resin 4: the LLDPE based on octene, overall I 2(190 ℃ of .2.16KG) is 0.85g/10min.And total body density is 0.918g/cm 3; The resin 4 of 41.4wt.% has 0.898g/cm 3density and the MI of 0.27g/10min and the resin 4 of 58.6wt.% there is 0.929g/cm 3density and the MI of 9.24g/10min; Resin 4 is according to United States Patent (USP) 5,844, the instruction preparation of 045 people such as () Kolthammer;
Comparative resin 5: the LLDPE based on octene prepared by double reaction device solution method.I 2(190℃.2.16KG)：1.3g/10min。Density: 0.941g/cm 3, the polymkeric substance in the first reactor is 25.92.%, density is 0.924g/cm 3and MI is 0.65g/10min; Polymkeric substance in the second reactor is 74.08%, and density is 0.947g/cm 3, MI is 5.45g/10min;
Comparative resin 6: the LLDPE based on octene prepared by solution method and Z-N catalyzer.I 2(190℃.2.16KG)：1g/10min。Density: 0.925g/cm 3.
Create conditions:
Comparative Examples 6: by 140 micron membranes of 100% comparative resin 6 preparations
Comparative Examples 2: by 45 micron membranes of 100% resin 1 preparation of the present invention
Comparative Examples 3: by comparative resin 2/ comparative resin 5/ comparative resin 2 (layer ratio: 120 micron membranes that 1/3/1) prepare
Comparative Examples 4: by comparative resin 4/ comparative resin 5/ comparative resin 4 (layer ratio: 120 micron membranes that 1/3/1) prepare
Comparative Examples 5: by comparative resin 2/ comparative resin 3/ comparative resin 2 (layer ratio: 120 micron membranes that 1/3/1) prepare
The embodiment of the present invention 1: by resin 1/ comparative resin 3/ of the present invention resin 1 of the present invention (layer ratio: 120 micron membranes that 1/3/1) prepare
The embodiment of the present invention 2: by resin 2/ comparative resin 3/ of the present invention resin 2 of the present invention (layer ratio: 120 micron membranes that 1/3/1) prepare
In Reifenhauser blown film production line, prepared by all films
Melt temperature: 220 ℃
Blow-up ratio: 2.2/1
Die head gap: 2.59mm
Result in table 3 shows:
1. with comparative film 1, compare, film 1 of the present invention has higher density (higher crystalline fraction) and suitable rigidity (modulus) with it, but it has 300% than low haze and 70% dart impact property improvement.
2. with comparative film 1, compare, film 2 of the present invention has the rigidity of low density slightly and low 10%, but it have 300% than the higher dart impact of low haze and 3.3 times.
3. comparative film 2 is simple by the first claimed interpretation preparation, although it has low global density and, than low modulus, has 45 micron membranes, it is only 27% thickness of film 1 of the present invention and 2, but its mist degree is close to 120 microns films of the present invention.
4. all comparative film 3,4,5 are compared with comparative film 1 and are had significantly than low haze, and it even has rigidity and the overall film density of improvement.This proof, the coextrusion of MDPE and LLDPE can reduce the film mist degree and therefore improve the film transparency.
5. all comparative film 3,4,5 are compared and are had significantly higher mist degree with film of the present invention, although their rigidity and density are only slightly high.This proof, in sandwich layer and cortex, the selection of resin is also important for manufacturing the high rigid film of high transparent.Use the rigid film that the first interpretation LLDPE (it has the high MW high-density fraction of low percentage ratio) obtains the dart impact with improvement of the best transparency in cortex.
6. for the comparative film 3,4,5 with suitable with it rigidity and density, 5 have minimum mist degree, are then 3,4 to have the highest mist degree.The co-extruded films prepared with MDPE with LLDPE by having low MW HDF is compared, and the co-extruded films prepared by the LLDPE with high MW HDF and MDPE has the better transparency.In the situation that have same resin in cortex, the mist degree of embodiment 3 is higher than the mist degree of embodiment 5.

Claims (15)

1. a multilayer film, comprise at least two layers, and the first interpretation that wherein the first layer comprises ethene and at least one alpha-olefin, be characterised in that wherein said the first interpretation has the 0.925g/cm of being less than 3density, and average M vand the paddy temperature T between described interpretation and high crystalline fraction hc, make from ATREF higher than T hcthe average M of fraction vaverage M divided by the whole polymkeric substance from ATREF v, i.e. M hc/ M hpbe less than 1.95 and wherein said the first interpretation there is the composition Tile Width index that is less than 60%, and the second interpretation that wherein at least one other second layer comprises ethene and optional at least one alpha-olefin, wherein said the second interpretation has 0.925-0.965g/cm 3density, wherein said Mv is the viscosity-average molecular weight from ATREF.
2. the film of claim 1, wherein said the first interpretation is non-homogeneous branching.
3. the film of claim 1, wherein said the first interpretation has the composition Tile Width index that is less than 55%.
4. the film of claim 1, wherein said the first interpretation has the M that is less than 1.7 hc/ M hp.
5. the film of claim 1, wherein said the second interpretation has higher than the density of 0.925g/cc and the MI of 0.1-10g/10 minute.
6. the film of claim 1, wherein said the second polymkeric substance is the non-homogeneous polymkeric substance that is selected from LLDPE and HDPE.
7. the film of claim 1, it also comprises at least one other natural or synthetic polymer.
8. the film of claim 7, wherein said synthetic polymer is Low Density Polyethylene.
9. the film of claim 1, wherein said the first interpretation has the melt index of 0.1g/10min to 10g/10min.
10. the film of claim 1, wherein said the first interpretation has the 0.922g/cm of being less than 3global density.
11. the film of claim 1, wherein said the first interpretation has every 1000 long chain branches that the C atom is less than 1.
12. the film of claim 1, wherein said the first interpretation has the molecular weight distribution M that is less than 5 w/ M n.
13. the goods of the film that comprises claim 1.
14. the film of claim 1, wherein said the first interpretation is crosslinked at least partly, reaches at least 5 % by weight gellings.
15. the film of claim 1, the dart B of at least 250 grams that wherein said film has the thickness of 120 microns and uses ASTM D1709 to measure, according to ASTM D1003, measure be less than 16% haze percentages and 2% secant modulus of at least 240MPa that pass through (MD+CD)/2 calculating measured according to ASTM D882.
CN2009801595952A 2009-03-31 2009-12-16 Film made from heterogeneous ethylene/alpha-olefin interpolymer Active CN102449003B (en)

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